CN107394161A - Compound silicon based electrode material, preparation method and applications - Google Patents
Compound silicon based electrode material, preparation method and applications Download PDFInfo
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- CN107394161A CN107394161A CN201710608818.5A CN201710608818A CN107394161A CN 107394161 A CN107394161 A CN 107394161A CN 201710608818 A CN201710608818 A CN 201710608818A CN 107394161 A CN107394161 A CN 107394161A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to electrode material field, specifically, there is provided a kind of compound silicon based electrode material, preparation method and applications.The compound silicon based electrode material is mainly made up of the silicon substrate core of prelithiation with the graphene layer being coated on the outside of the silicon substrate core of prelithiation.The compound silicon based electrode material has environmental stability height, the advantages of good inertia, first coulombic efficiency height and good cycling stability is showed to solvent, more than 24h is deposited in air not change, coulombic efficiency is up to more than 90% first, good inertia is presented to water solvent and oily series solvent, capability retention is more than 92% after 20 circulations.
Description
Technical field
The present invention relates to electrode material field, in particular to a kind of compound silicon based electrode material, preparation method and its
Using.
Background technology
Rechargeable lithium ion batteries have, good cycling stability higher than energy, operating temperature range is wide, self-discharge rate is low and
The advantages that environment compatibility is good, have been widely used for portable electric appts, mobile communication, electric tool, intelligent appliance etc.
Field, and progressively extend to hybrid vehicle, plug-in electric car, pure electric automobile, power network energy storage and regenerative resource storage
The fields such as energy.Existing commercial Li-ion battery is mainly using carbon-based material as negative active core-shell material, particularly graphite-like material
Material, the theoretical electrochemistry finite capacity of such material, only 372mAh/g, it is difficult to meet that lithium ion battery further improves energy
The requirement of density.Therefore, researching and developing novel high-capacity negative material turns into the key for promoting lithium ion battery sustainable development.
Silicon materials are a kind of lithium ion battery negative materials of high power capacity, due to the capacity (4200mAh/g) of its superelevation, quilt
Think that traditional commercialization graphite cathode can be substituted.But silicon based anode material Volume Changes huge during removal lithium embedded (>
300%) cause its easily efflorescence, come off, electrode cycle performance extreme difference；And silicon-based anode is also asked in the presence of coulombic efficiency is low first
Topic.Prior art improves the coulombic efficiency first of silica-base material by prelithiation, however, prelithiation electrode material and shakiness
Fixed, this unstability includes depositing unstable, unstable for the solvent in battery assembly technology and filling in the environment
Capacity is unstable during discharge cycles, and which suppress the development of silicon based electrode material.Therefore, a kind of prelithiation of stabilization is developed
Silicon based electrode material is very necessary.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of compound silicon based electrode material, and the compound silicon based electrode material has ring
Border stability height, the advantages of good inertia, first coulombic efficiency height and good cycling stability is showed to solvent.
The second object of the present invention is to provide a kind of preparation method of compound silicon based electrode material, this method preparation technology
Simply, controllability is high, is adapted to industrial continuous production, the compound silicon based electrode material being prepared have environmental stability it is high,
The advantages of good inertia, first coulombic efficiency height and good cycling stability are showed to solvent.
The third object of the present invention in providing a kind of application of above-mentioned compound silicon based electrode material in lithium ion battery,
Above-mentioned compound silicon based electrode materials application can be improved to the coulombic efficiency first and stable circulation of battery in lithium ion battery
Property.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
In a first aspect, the invention provides a kind of compound silicon based electrode material, mainly by the silicon substrate core and cladding of prelithiation
Graphene layer on the outside of the silicon substrate core of prelithiation is formed.
As further preferably technical scheme, the silicon substrate core of the prelithiation mainly prepared by silicon source and containing lithium reagent and
Into.
As further preferably technical scheme, the silicon source is Si and/or SiO, it is described containing lithium reagent be LiH and/or
Li；
Preferably, the particle diameter of the silicon source is 10nm-100 μm.
As further preferably technical scheme, the silicon source and the mass ratio containing lithium reagent are (3-7)：1.
As further preferably technical scheme, the graphene layer is mainly made up of the graphene of 1-10 layers.
Second aspect, the invention provides a kind of preparation method of compound silicon based electrode material, comprise the following steps：First
Oxidation processes are carried out to the silicon substrate core of prelithiation, carbon coating is then carried out again, graphene is formed on the outside of the silicon substrate core of prelithiation
The compound silicon based electrode material is can obtain after layer.
As further preferably technical scheme, oxidation processes are carried out in weak oxide atmosphere, in the weak oxide atmosphere
O2Volume fraction be 1%-10%；
Preferably, the oxidizing temperature of oxidation processes is 400-1000 DEG C, oxidization time 5-300min, in weak oxide atmosphere
The volume flow of gas is 1-100sccm.
As further preferably technical scheme, the carbon coating uses chemical vapour deposition technique；
Preferably, the reaction temperature of chemical vapour deposition technique is 300-1100 DEG C, reaction time 10-360min；
Preferably, chemical vapour deposition technique is to carry out chemical vapour deposition reaction under an inert atmosphere, wherein, the body of carbon source
Product accounts for the 0.5%-30% of carbon source and inert gas cumulative volume；
Preferably, carbon source be methane, ethene, propylene, acetylene, alcohol vapor and benzoic acid steam in any one or extremely
Few two kinds combination.
As further preferably technical scheme, the silicon substrate core of the prelithiation is mainly prepared by following methods：Will
Well mixed silicon source and calcined containing lithium reagent, then crush, obtain the silicon substrate core of prelithiation；
Preferably, calcining heat is 400-1000 DEG C, and calcination time 10-120min, calcination atmosphere is inert atmosphere.
The third aspect, the invention provides a kind of application of above-mentioned compound silicon based electrode material in lithium ion battery.
Compared with prior art, beneficial effects of the present invention are：
Compound silicon based electrode material provided by the invention mainly by prelithiation silicon substrate core and be coated on the silicon substrate of prelithiation
Graphene layer on the outside of core is formed, and graphene is a kind of two-dimentional carbon material, and it has impermeability, i.e., in addition to proton, other
Material cannot pass through graphene, have the function that waterproof, impermeable oxygen, carbon dioxide etc., therefore it is multiple to improve this
Close the stability of silicon based electrode material：First, the material has environmental stability, deposits more than 24h in atmosphere and does not become
Change；Secondly, the compound silicon based electrode material has solvent inertia, and whether for oily series solvent or water solvent, it is high first
Secondary coulombic efficiency does not reduce.In addition, the silicon substrate core of prelithiation enables to silicon substrate core that volumetric expansion occurs, filled first
Stable interface can be formed in discharge cycles, effectively reduces volume change of the material in removal lithium embedded, therefore can be effective
Suppress the decay of capacity, good cycling stability.
The preparation method technique of compound silicon based electrode material provided by the invention is simple, and controllability is high, is adapted to industry continuous
Metaplasia is produced, and carries out oxidation processes to the silicon substrate core of prelithiation first, the silicon substrate core surface of prelithiation is formed oxide layer, is graphite
Alkene provides substantial amounts of nuclearing centre, for the nucleating growth of graphene, then carries out carbon coating again, obtains the compound silicon substrate electricity
Pole material, the compound silicon based electrode material being prepared using this method are had environmental stability height, solvent are showed well
Inertia, coulombic efficiency is high first and the advantages of good cycling stability.
By above-mentioned compound silicon based electrode materials application can be improved in lithium ion battery battery coulombic efficiency first and
Cyclical stability, therefore, it is possible to give full play to the advantage of the height ratio capacity of compound silicon based electrode material, actual application value is more
Height, is adapted to commercially produce and extensive use.
Brief description of the drawings
Fig. 1 is the XRD spectrum of the silicon monoxide before and after prelithiation in embodiment 1；
Fig. 2 is the SEM figures of compound silicon based electrode material in embodiment 1；
Fig. 3 is the TEM figures of compound silicon based electrode material in embodiment 1；
Fig. 4 is the coulombic efficiency figure first of compound silicon based electrode material in embodiment 1；
Fig. 5 is the circulation stability diagram of compound silicon based electrode material in embodiment 1；
Fig. 6 is the air shelf stability figure of compound silicon based electrode material in embodiment 1；
Fig. 7 is the solvent stability figure of compound silicon based electrode material in embodiment 1.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.
In a first aspect, the invention provides a kind of compound silicon based electrode material, mainly by the silicon substrate core and cladding of prelithiation
Graphene layer on the outside of the silicon substrate core of prelithiation is formed.
In lithium ion battery, the efficiency for charge-discharge of negative pole is low can cause positive pole active lithium-ion be embedded in negative pole after,
During electric discharge can not whole deintercalations, some lithium ion, which " is absorbed in " in negative pole, turns into " dead lithium ", be no longer participate in electrochemistry circulation, from
And reduce the ratio energy of battery.The coulombic efficiency first of silicon based anode material is generally below 70%, following cycle efficiency also below
99%, hence it is evident that less than the index of graphite negative electrodes, cause the height ratio capacity advantage of silicon based anode material can not give full play to.
Compound silicon based electrode material provided by the invention mainly by prelithiation silicon substrate core and be coated on the silicon substrate of prelithiation
Graphene layer on the outside of core is formed, and graphene is a kind of two-dimentional carbon material, and it has impermeability, i.e., in addition to proton, other
Material cannot pass through graphene, have the function that waterproof, impermeable oxygen, carbon dioxide etc., therefore it is multiple to improve this
Close the stability of silicon based electrode material：First, the material has environmental stability, deposits more than 24h in atmosphere and does not become
Change；Secondly, the compound silicon based electrode material has solvent inertia, and whether for oily series solvent or water solvent, it is high first
Secondary coulombic efficiency does not reduce.In addition, the silicon substrate core of prelithiation enables to silicon substrate core that volumetric expansion occurs, filled first
Stable interface can be formed in discharge cycles, effectively reduces volume change of the material in removal lithium embedded, therefore can be effective
Suppress the decay of capacity, good cycling stability.
Be preferably carried out in one kind in mode, the silicon substrate core of the prelithiation mainly prepared by silicon source and containing lithium reagent and
Into.
It should be noted that silicon source can be arbitrary existing siliceous electroactive substance, such as Si, SiOC or SiOx
(0<x<At least one of 2), wherein, SiOxIn x it is typical but non-limiting be 0.2,0.4,0.6,0.8,1,1.2,
1.4th, 1.6 or 1.8；Can be LiH and/or Li containing lithium reagent.
It is preferably carried out in one kind in mode, the silicon source is Si and/or SiO, and described containing lithium reagent is LiH and/or Li.
Preferably, the particle diameter of the silicon source is 10nm-100 μm.In the present invention, silicon source is typical but non-limiting to be：
10nm, 20nm, 40nm, 60nm, 80nm, 100nm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or
100μm.Preferably, the particle diameter of the silicon source is 20nm-80 μm；It is further preferred that the particle diameter of the silicon source is 60nm-60 μ
m。
It is preferably carried out in one kind in mode, the silicon source and the mass ratio containing lithium reagent are (3-7)：1.The present invention
In, silicon source is typical but non-limiting with the mass ratio containing lithium reagent to be：3:1、4:1、5:1、6:1 or 7:1.Aforementioned proportion is preferred
For (4-7)：1, more preferably (4-6)：1.
It is preferably carried out in one kind in mode, the graphene layer is mainly made up of the graphene of 1-10 layers.
Second aspect, the invention provides a kind of preparation method of compound silicon based electrode material, comprise the following steps：First
Oxidation processes are carried out to the silicon substrate core of prelithiation, carbon coating is then carried out again, graphene is formed on the outside of the silicon substrate core of prelithiation
The compound silicon based electrode material is can obtain after layer.The preparation method technique of above-mentioned compound silicon based electrode material is simple, controllable
Property it is high, be adapted to industrial continuous production, oxidation processes carried out to the silicon substrate core of prelithiation first, make the silicon substrate core surface of prelithiation
Oxide layer is formed, substantial amounts of nuclearing centre is provided for graphene, for the nucleating growth of graphene, then carries out carbon coating again,
The compound silicon based electrode material is obtained, the compound silicon based electrode material being prepared using this method has environmental stability
Height, the advantages of good inertia, first coulombic efficiency height and good cycling stability is showed to solvent.
It is preferably carried out in one kind in mode, oxidation processes are carried out in weak oxide atmosphere, O in the weak oxide atmosphere2
Volume fraction be 1%-10%.In the present invention, O in weak oxide atmosphere2Volume fraction typical but non-limiting be：1%th,
2%th, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.Above-mentioned volume fraction is preferably 2%-9%, more preferably
3%-8%.
Optionally, above-mentioned weak oxide atmosphere can be O2And CO2Gaseous mixture, or O2With the gaseous mixture of argon gas.
Preferably, the oxidizing temperature of oxidation processes is 400-1000 DEG C, oxidization time 5-300min, in weak oxide atmosphere
The volume flow of gas is 1-100sccm.In the present invention, oxidizing temperature is typical but non-limiting to be：400℃、500℃、600
DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C；Oxidization time is typical but non-limiting to be：5min、10min、30min、
60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min or 300min；Volume flow typical case but
It is nonrestrictive to be：1sccm、5sccm、10sccm、15sccm、20sccm、25sccm、30sccm、35sccm、40sccm、
45sccm、50sccm、55sccm、60sccm、65sccm、70sccm、75sccm、80sccm、85sccm、90sccm、95sccm
Or 100sccm.
It is preferably carried out in one kind in mode, the carbon coating uses chemical vapour deposition technique.
Preferably, the reaction temperature of chemical vapour deposition technique is 300-1100 DEG C, reaction time 10-360min.This hair
In bright, the reaction temperature of chemical vapour deposition technique is typical but non-limiting to be：300℃、400℃、500℃、600℃、700
DEG C, 800 DEG C, 900 DEG C, 1000 DEG C or 1100 DEG C；Reaction time is typical but non-limiting to be：10min、20min、30min、
40min、50min、60min、70min、80min、90min、100min、110min、120min、150min、180min、
210min, 240min, 270min, 300min, 330min or 360min.Preferably, above-mentioned reaction temperature is 400-1000 DEG C, instead
It is 20-330min between seasonable；It is further preferred that above-mentioned reaction temperature is 500-900 DEG C, reaction time 30-300min.
Preferably, chemical vapour deposition technique is to carry out chemical vapour deposition reaction under an inert atmosphere, wherein, the body of carbon source
Product accounts for the 0.5%-30% of carbon source and inert gas cumulative volume.In the present invention, the volume of typical but non-limiting carbon source accounts for carbon
Source and inert gas cumulative volume 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%,
22%th, 24%, 26%, 28% or 30%.
It should be noted that above-mentioned inert atmosphere can select arbitrary inert atmosphere, such as can be：Argon gas, nitrogen,
At least one of carbon dioxide or hydrogen.
Preferably, carbon source be methane, ethene, propylene, acetylene, alcohol vapor and benzoic acid steam in any one or extremely
Few two kinds combination.In the present invention, typical but non-limiting carbon source is：Methane, ethene, propylene, acetylene, alcohol vapor, benzene
The combination of the combination of formic acid steam, methane and ethene, propylene and acetylene, the combination of alcohol vapor and benzoic acid steam, methane, second
The combination of alkene and propylene, the combination of acetylene, alcohol vapor and benzoic acid steam etc..
Preferably, when carrying out chemical vapor deposition using low pressure chemical vapor deposition equipment, the chemical vapor deposition
The vacuum of reaction is 1-1000Pa；Vacuum it is typical but non-limiting for 1Pa, 10Pa, 100Pa, 200Pa, 300Pa,
400Pa, 500Pa, 600Pa, 700Pa, 800Pa, 900Pa or 1000Pa.
It is preferably carried out in one kind in mode, the silicon substrate core of the prelithiation is mainly prepared by following methods：Will be mixed
Close uniform silicon source and calcined containing lithium reagent, then crush, obtain the silicon substrate core of prelithiation.
Preferably, calcining heat is 400-1000 DEG C, and calcination time 10-120min, calcination atmosphere is inert atmosphere.This
In invention, calcining heat is typical but non-limiting to be：400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000
℃；Calcination time is typical but non-limiting to be：10min、20min、30min、40min、50min、60min、70min、
80min, 90min, 100min, 110min or 120min.Preferably, above-mentioned calcining heat is 500-900 DEG C, and calcination time is
20-110min；It is further preferred that above-mentioned calcining heat is 600-800 DEG C, reaction time 30-100min.
It should be noted that above-mentioned inert atmosphere can select arbitrary inert atmosphere, such as can be：Argon gas and/or
Hydrogen.
Preferably, in preparation method provided by the present invention, the reaction of involved oxidizing temperature, chemical vapour deposition technique
The heating rate of temperature and calcining heat in practical operation is 5-30 DEG C/min, typical but non-limiting heating rate
For：5 DEG C/min, 10 DEG C/min, 15 DEG C/min, 20 DEG C/min, 25 DEG C/min or 30 DEG C/min.
The third aspect, the invention provides a kind of application of above-mentioned compound silicon based electrode material in lithium ion battery.Will
Above-mentioned compound silicon based electrode materials application can improve the coulombic efficiency first and cyclical stability of battery in lithium ion battery,
Therefore, it is possible to give full play to the advantage of the height ratio capacity of compound silicon based electrode material, actual application value is higher, is adapted to commercialization
Production and extensive use.
It should be noted that the lithium ion for including above-mentioned compound silicon based electrode material is prepared using the conventional method of this area
Battery.
With reference to embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
A kind of compound silicon based electrode material, mainly by prelithiation silicon substrate core and be coated on the outside of the silicon substrate core of prelithiation
Graphene layer is formed, and the silicon substrate core of the prelithiation is mainly prepared by silicon source and containing lithium reagent.
Above-mentioned compound silicon based electrode material is mainly prepared by following methods：
(a) silicon monoxide powder (particle diameter be 5 μm) is well mixed in mortar with LiH, mass ratio 7:1, it is placed in often
In pressure-pipe type stove under an argon atmosphere, 800 DEG C of calcining 1h, obtain the silicon substrate core of prelithiation, its XRD is as shown in Figure 1；
(b) the silicon substrate core for the prelithiation for obtaining step (a) carries out oxidation processes, weak oxide atmosphere in weak oxide atmosphere
For O2With the gaseous mixture of argon gas, wherein O2Volume fraction be 1%, the flow of gaseous mixture is 100sccm；Oxidizing temperature is 1000
DEG C, oxidization time 10min；
(c) the silicon substrate core of the prelithiation in step (b) Jing Guo oxidation processes is put into quartz boat, and is put into chemical gaseous phase
Deposit in stove, the equipment is heated to 1000 DEG C with 20 DEG C/min heating rate, is then passed through first under argon gas, hydrogen shield
(gaseous mixture of argon gas and hydrogen also serves as the carrier gas of methane to alkane, and methane volumetric accounts for the 0.5%) progress of methane and carrier gas cumulative volume
Reaction, methane carry out chemisorbed, nucleation and growth, reaction time with vapor reaction presoma on the silicon substrate core surface of prelithiation
For 60min；
(d) after reaction terminates, treat that equipment is cooled to 25 DEG C, obtain black powder material, i.e., compound silicon based electrode material, its
Microscopic appearance figure is as shown in Fig. 2 the high resolution transmission electron microscopy of graphene layer is as shown in Figure 3.
Embodiment 2
A kind of compound silicon based electrode material, mainly by prelithiation silicon substrate core and be coated on the outside of the silicon substrate core of prelithiation
Graphene layer is formed, and the silicon substrate core of the prelithiation is mainly prepared by silicon source and containing lithium reagent.
Above-mentioned compound silicon based electrode material is mainly prepared by following methods：
(a) silicon monoxide powder (particle diameter 10nm) is well mixed in mortar with LiH, mass ratio 3:1, it is placed in often
In pressure-pipe type stove under an argon atmosphere, 400 DEG C of calcining 2h；
(b) the silicon substrate core for the prelithiation for obtaining step (a) carries out oxidation processes, weak oxide atmosphere in weak oxide atmosphere
For O2With the gaseous mixture of argon gas, wherein O2Volume fraction be 10%, the flow of gaseous mixture is 20sccm；Oxidizing temperature is 400
DEG C, oxidization time 5min；
(c) the silicon substrate core of the prelithiation in step (b) Jing Guo oxidation processes is put into quartz boat, and is put into chemical gaseous phase
Deposit in stove, the equipment is heated to 300 DEG C with 5 DEG C/min heating rate, is then passed through methane under argon gas, hydrogen shield
(gaseous mixture of argon gas and hydrogen also serves as the carrier gas of methane, and methane volumetric accounts for methane and the 30%) progress of carrier gas cumulative volume is anti-
Should, methane is in the silicon substrate core surface of prelithiation progress chemisorbed, nucleation and growth, reaction time with vapor reaction presoma
360min；
(d) after reaction terminates, treat that equipment is cooled to 25 DEG C, obtain black powder material, i.e., compound silicon based electrode material.
Embodiment 3
A kind of compound silicon based electrode material, mainly by prelithiation silicon substrate core and be coated on the outside of the silicon substrate core of prelithiation
Graphene layer is formed, and the silicon substrate core of the prelithiation is mainly prepared by silicon source and containing lithium reagent.
Above-mentioned compound silicon based electrode material is mainly prepared by following methods：
(a) silicon monoxide powder (particle diameter be 10 μm) is well mixed in mortar with LiH, mass ratio 5:1, it is placed in often
In pressure-pipe type stove under an argon atmosphere, 1000 DEG C of calcining 10min；
(b) the silicon substrate core for the prelithiation for obtaining step (a) carries out oxidation processes, weak oxide atmosphere in weak oxide atmosphere
For O2With the gaseous mixture of argon gas, wherein O2Volume fraction be 5%, the flow of gaseous mixture is 50sccm；Oxidizing temperature is 700 DEG C,
Oxidization time is 240min；
(c) the silicon substrate core of the prelithiation in step (b) Jing Guo oxidation processes is put into quartz boat, and is put into chemical gaseous phase
Deposit in stove, the equipment is heated to 800 DEG C with 30 DEG C/min heating rate, is then passed through first under argon gas, hydrogen shield
(gaseous mixture of argon gas and hydrogen also serves as the carrier gas of methane to alkane, and methane volumetric accounts for methane and the 15%) progress of carrier gas cumulative volume is anti-
Should, methane is in the silicon substrate core surface of prelithiation progress chemisorbed, nucleation and growth, reaction time with vapor reaction presoma
180min；
(d) after reaction terminates, treat that equipment is cooled to 25 DEG C, obtain black powder material, i.e., compound silicon based electrode material.
Comparative example 1
Silicon monoxide electrode material.
Comparative example 2
A kind of silicon based electrode material, is mainly prepared by following methods：
Silicon monoxide powder (particle diameter be 100 μm) is well mixed in mortar with LiH, mass ratio 7:1, it is placed in normal pressure
In tube furnace under an argon atmosphere, 800 DEG C of calcining 1h, obtain the silicon based electrode material.
Comparative example 3
A kind of compound silicon based electrode material, by nano silicon spheres powder (particle diameter 20nm) and it is coated on nano silicon spheres powder surface
Carbon-coating is formed, and is mainly prepared by following methods：Nano silicon spheres powder is put into quartz boat, and is put into chemical vapor deposition stove
In, the equipment is heated to 1000 DEG C with 20 DEG C/min heating rate, be then passed through under argon gas, hydrogen shield methane (argon gas,
The gaseous mixture of hydrogen also serves as the carrier gas of methane, and methane volumetric accounts for 0.5%) being reacted for methane and carrier gas cumulative volume, reacts
Time is 60min.
Performance test
Respectively using the electrode material in embodiment 1-3 and comparative example 1-3 as negative pole, lithium ion battery is prepared, and test it
The performance of lithium ion battery：Each electrode material, conductive agent, organic solvent are mixed and are made into slurry, is coated on copper and is used as negative pole,
Half-cell is assembled into as positive pole using lithium piece and tests its cycle performance, as a result as shown in table 1.
The battery performance circulation result of first week of the compound silicon based electrode material that embodiment 1 is provided as shown in figure 4, its
Coulombic efficiency is 90.6% first, and reversible capacity is 1250mAh/g first；Circulation performance is as shown in figure 5, circulate 20 times
Afterwards, capability retention 92%；Environmental stability as shown in fig. 6, as we know from the figure the material store in atmosphere 12h, 24h or
Coulombic efficiency does not change substantially first after 48h, illustrates that environmental stability is good；The material is illustrated in figure 7 to assemble electrode
The stability of the solvent of process, it can be seen that whether oil system PVDF or water system LA132, there is higher coulomb first
Efficiency, solvent stability are high.
The half-cell the performance test results of table 1
From the performance test results of table 1, the coulombic efficiency first of embodiment 1-3 electrode material, first reversible appearance
Capability retention after amount, 20 circulations, deposit the coulombic efficiency first after 48h in air and solvent stability is superior to pair
Ratio 1-3, thus illustrates, compound silicon based electrode material provided by the invention has given full play to the advantage in its structure, have compared with
High coulombic efficiency first and reversible capacity, and good cycling stability, environmental stability are high, it is good to be showed to solvent first
Inertia, the high power capacity advantage of silicon materials can be given full play to, be adapted to commercial applications, high financial profit.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
- A kind of 1. compound silicon based electrode material, it is characterised in that mainly by prelithiation silicon substrate core and be coated on the silicon of prelithiation Graphene layer on the outside of base core is formed.
- 2. compound silicon based electrode material according to claim 1, it is characterised in that the silicon substrate core of the prelithiation mainly by Silicon source and it is prepared containing lithium reagent.
- 3. compound silicon based electrode material according to claim 2, it is characterised in that the silicon source is Si and/or SiO, institute It is LiH and/or Li to state containing lithium reagent；Preferably, the particle diameter of the silicon source is 10nm-100 μm.
- 4. compound silicon based electrode material according to claim 3, it is characterised in that the silicon source is with described containing lithium reagent Mass ratio is (3-7)：1.
- 5. the compound silicon based electrode material according to claim any one of 1-4, it is characterised in that the graphene layer is main It is made up of the graphene of 1-10 layers.
- 6. the preparation method of the compound silicon based electrode material described in claim any one of 1-5, it is characterised in that including following step Suddenly：Oxidation processes are carried out to the silicon substrate core of prelithiation first, carbon coating is then carried out again, is formed on the outside of the silicon substrate core of prelithiation The compound silicon based electrode material is can obtain after graphene layer.
- 7. the preparation method of compound silicon based electrode material according to claim 6, it is characterised in that oxidation processes are in weak oxygen Change and carried out in atmosphere, O in the weak oxide atmosphere2Volume fraction be 1%-10%；Preferably, the oxidizing temperature of oxidation processes is 400-1000 DEG C, oxidization time 5-300min, gas in weak oxide atmosphere Volume flow be 1-100sccm.
- 8. the preparation method of compound silicon based electrode material according to claim 6, it is characterised in that the carbon coating uses Chemical vapour deposition technique；Preferably, the reaction temperature of chemical vapour deposition technique is 300-1100 DEG C, reaction time 10-360min；Preferably, chemical vapour deposition technique is to carry out chemical vapour deposition reaction under an inert atmosphere, wherein, the volume of carbon source accounts for The 0.5%-30% of carbon source and inert gas cumulative volume；Preferably, carbon source is any one in methane, ethene, propylene, acetylene, alcohol vapor and benzoic acid steam or at least two The combination of kind.
- 9. the preparation method of the compound silicon based electrode material according to claim any one of 6-8, it is characterised in that described pre- The silicon substrate core of lithiumation is mainly prepared by following methods：Calcined by well mixed silicon source and containing lithium reagent, then crush, obtain To the silicon substrate core of prelithiation；Preferably, calcining heat is 400-1000 DEG C, and calcination time 10-120min, calcination atmosphere is inert atmosphere.
- 10. application of the compound silicon based electrode material in lithium ion battery described in claim any one of 1-5.
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| CN109616700A (en) * | 2018-11-29 | 2019-04-12 | 溧阳天目先导电池材料科技有限公司 | A kind of modified prelithiation material and preparation method thereof and lithium battery |
| CN111326727A (en) * | 2020-03-09 | 2020-06-23 | 洛阳联创锂能科技有限公司 | Multi-component silicon-oxygen negative electrode material for lithium ion battery and preparation method thereof |
| CN111900368A (en) * | 2020-07-24 | 2020-11-06 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion battery-grade silicon monoxide negative electrode material, and preparation method and application thereof |
| CN111900369A (en) * | 2020-07-24 | 2020-11-06 | 陕西煤业化工技术研究院有限责任公司 | Pre-lithiated silicon oxide/carbon composite material and preparation method and application thereof |
| CN112072072A (en) * | 2019-06-10 | 2020-12-11 | 通用汽车环球科技运作有限责任公司 | Pre-cycled silicon electrode |
| CN112271289A (en) * | 2020-10-30 | 2021-01-26 | 陕西煤业化工技术研究院有限责任公司 | High-first-efficiency pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof |
| CN112670453A (en) * | 2020-12-23 | 2021-04-16 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based laminated anode material and preparation method and application thereof |
| CN112701267A (en) * | 2020-12-30 | 2021-04-23 | 湖州杉杉新能源科技有限公司 | Pre-lithiated silica composite material, negative pole piece, lithium battery and preparation method of pre-lithiated silica composite material |
| CN115036485A (en) * | 2022-06-24 | 2022-09-09 | 中山烯利来设备科技有限公司 | Manufacturing method of silicon-carbon cathode |
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| CN109616700A (en) * | 2018-11-29 | 2019-04-12 | 溧阳天目先导电池材料科技有限公司 | A kind of modified prelithiation material and preparation method thereof and lithium battery |
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| CN112701267A (en) * | 2020-12-30 | 2021-04-23 | 湖州杉杉新能源科技有限公司 | Pre-lithiated silica composite material, negative pole piece, lithium battery and preparation method of pre-lithiated silica composite material |
| CN115036485A (en) * | 2022-06-24 | 2022-09-09 | 中山烯利来设备科技有限公司 | Manufacturing method of silicon-carbon cathode |
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